Aromatic Sulfonic Acids Research Articles

Selective adsorption of aromatic sulfonic acid from wastewater using a surface imprinted polymer: H‐acid as a representative contaminant

Selective adsorption of aromatic sulfonic acid from wastewater using a surface imprinted polymer: H‐acid as a representative contaminant

The Effect of Anion Modification on the Conductive Polymer/Ag‐Interdigitated Electrodes Micro‐Supercapacitor

Due to their outstanding electrical conductivity, simplicity of synthesis, and exceptional flexibility, conductive polymers are the most attractive electrode materials for micro‐supercapacitors (MSCs). However, when used as an electrode material alone, its poor capacitive performance and cycle‐life hinder the wide engineering applications. Herein, a polypyrrole (PPy)/Ag‐interdigitated electrodes MSCs is proposed, and the impact of aromatic sulfonic acid group anion modification on the electrochemical properties and flexibility of PPy/Ag MSCs is investigated. In the results, it is shown that different aromatic sulfonic‐acid‐based anionic dopants have different effects on the properties of PPy films. Among the prepared three PPy/Ag MSCs devices, PPy:anthraquinone‐2‐sulfonic acid/Ag MSCs have the highest areal capacitance (198.8 mF cm−2) at a current density of 0.5 mA cm−2, surpassing PPy:2‐naphthalenesulfonic acid/Ag MSCs (114.3 mF cm−2) and PPy:p‐toluenesulfonic acid monohydrate/Ag MSCs (89.7 mF cm−2). Furthermore, at a power density of 0.25 mW cm−2, the PPy:AQS/Ag MSCs exhibit a high energy density of 27.61 μWh cm−2, which is above the most of the previously reported PPy‐based MSCs. Therefore, in this research, the groundwork is provided for improving properties of flexible MSCs based on PPy.

Carbon‐Sulfur Bond Formation via Ipso Nucleophilic Substitution of Electron‐Deficient Benzenesulfonic Acid with Thiol

AbstractDeveloping green and convenient strategies for constructing C−S bonds is attractive, as it is indispensable for numerous essential biological and pharmaceutical compound syntheses. Herein, an efficient, cost‐effective method for synthesizing 2,4‐dinitroaryl thioether derivatives is achieved by ipso nucleophilic substitution of an aromatic sulfonic acid group by thiol to construct a new C−S bond. This methodology neither requires the assistance of any transition metal catalyst nor harsh reaction conditions. Such thioether formation from aryl sulfonic acids is new.

Nano Pt/TiO2 photocatalyst for ultrafast production of sulfamic acid derivatives using 4-nitroacetanilides as nitrogen precursor in continuous flow reactors

The design of reactors based on high performance photocatalysts is an important research in catalytic hydrogenation. In this work, modification of titanium dioxide nanoparticles (TiO2 NPs) was achieved by preparation of Pt/TiO2 nanocomposites (NCs) through photo-deposition method. Both nanocatalysts were used for the photocatalytic removal of SOx from the flue gas at room temperature in the presence of hydrogen peroxide, water, and nitroacetanilide derivatives under visible light irradiation. In this approach, chemical deSOx was achieved along with protection of the nanocatalyst from sulfur poising through the interaction of the released SOx from SOx-Pt/TiO2 surface with p-nitroacetanilide derivatives to produce simultaneous aromatic sulfonic acids. Pt/TiO2 NCs have a bandgap of 2.64 eV in visible light range, which is lower than the bandgap of TiO2 NPs, whereas TiO2 NPs have a mean size of 4 nm and a high specific surface area of 226 m2/g. Pt/TiO2 NCs showed high photocatalytic sulfonation of some phenolic compounds using SO2 as a sulfonating agent along with the existence of p-nitroactanilide derivatives. The conversion of p-nitroacetanilide followed the combination processes of adsorption and catalytic oxidation–reduction reactions. Construction of an online continuous flow reactor–high-resolution time-of-flight mass spectrometry system had been investigated, realizing real-time and automatic monitoring of completion the reaction. 4-nitroacetanilide derivatives (1a-1e) was converted to its corresponding sulfamic acid derivatives (2a–2e) in 93–99% isolated yields of within 60 s. It is expected to offer a great opportunity for ultrafast detection of pharmacophores.

Ammonium-free and grain-protection deliming technology with the combination of aromatic sulfonic acid and sodium dihydrogen phosphate in leather manufacture

Ammonia-nitrogen, a grave environmental concern, is a typical pollutant in deliming process due to the inclusion of ammonium salts as deliming agents in leather manufacture. In order to reduce the emission of ammonia-nitrogen and improve the biological treatment of mixed tannery wastewater, an ammonium-free deliming method was designed and optimized based on the synergistic effects of aromatic sulfonic acids and sodium dihydrogen phosphate. The results indicated that, the penetrating and buffering performance of the mixtures of p-Hydroxybenzene sulfonic acid (pHBSA) and sodium dihydrogen phosphate (SDHP) at weight ratio of 2:1 was good enough to fulfill the requirement of deliming. The organoleptic and mechanical properties of the crust leather produced by pHBSA-SDHP mixtures deliming were similar with the conventional ammonium sulfate deliming, and the grain pattern was found to be protected against the damage caused by enzymes during bating. The concentrations of ammonia-nitrogen and total nitrogen in pHBSA-SDHP deliming effluent were dramatically cut down by 99% and 94%. It is anticipated that the mixed tannery wastewater could be disposed of more easily by means of adjusting the total organic ratios of C:N:P to their natural ratio by introducing an additional carbon and phosphorus source to the tannery wastewater. This investigation provides an improved method of leather making with significant reduction of ammonia nitrogen emission in deliming operation and fulfills the integral requirements of the modern sustainable leather industry.

Fabrication of Thermally Stable Sulfonated Poly(arylene ether sulfone) Containing Sulfonic Acid Based Additives for Proton Exchange Membrane Fuel Cells

AbstractA systematic investigations on the effect of sulfonic acid additives for the fabrication of thermally stable sulfonated poly(arylene ether sulfone) (PAES) composites for proton exchange membranes fuel cell applications were carried out. A uniform microstructure containing different concentration (1, 5 and 10 vol.%) of aromatic sulfonic acid additives (aniline‐2‐sulfonic acid (ASA), 3‐aminobenzenesulfonic acid (ABSA) and 3‐amino‐4‐hydroxy‐benzenesulfonic acid (AHBSA)) and biphenol‐based disulfonated poly(arylene ether sulfone) copolymer (PAES) as the matrix were successfully prepared. Phase segregation of the additives with sizes ranging from 1 to 2 μm was confirmed using scanning electron microscopy (SEM). Both thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC) confirmed that additive derived PAES were thermally stable up to 400 °C. Proton conductivity of ASA‐PAES membranes was found to increase gradually with ASA concentration. Among all membranes PAES‐10 %ASA exhibited the highest conductivity of 0.123±0.01 S⋅cm−1 at 100 % relative humidity. However, PAES‐1 %ASA and PAES‐10 %ABSA membranes demonstrated the lowest leaching. Water uptake, ion exchange capacity and leaching parameters were correlated to additive concentration. This study will serve as a guide for the fabrication of PAES membranes with high concentration of sulfonated group in the polymer chain with enhanced thermal stability and proton conductivity.

Effect of Pickling Materials on Leather Quality from a Hide Surface Charge Perspective

Salt-free pickling technology has recently received increased attention because it produces much lower salt pollution than the conventional pickling technology using formic acid, sulfuric acid, and sodium chloride. However, the existing salt-free pickling materials, for instance, aromatic sulfonic acids (ASAs), lead to reduced leather quality and the reason behind this phenomenon is unclear. In this study, we explored how ASAs affect the properties of tannedleather. Results showed that typical ASAs, such as 5-sulfosalicylic acid, 1,5-naphthalenedisulfonic acid, and 2-naphthalenesulfonic acid, penetrated cattle hide more slowly compared with formic and sulfuric acids because of their large molecular weight and strong intermolecular interactions with hide collagen. ASAs decreased the positive charge of the pickled hide via interactions with their sulfonic acid groups, resulting in the increased adsorption rate of chrometanning agent to the hide surface. Rapid tanning agent adsorption could impede the deep penetration and uniform distribution of the agent in the ASA-pickled hide. Thus, the properties of wet blues and crust leathers pickled with ASAs are inferior to those of wet blue and crust leather pickled using conventional pickling materials. Our results indicate that a strongly positive charge of the pickled hide is vital to obtaining high-quality leather and provide insights into salt-free pickling materials from a hide surface charge perspective.

Inside Cover: Porous Organic Salts: Diversifying Void Structures and Environments (Angew. Chem. Int. Ed. 31/2022)

Porous organic salts (POSs) are porous organic materials, in which various aromatic sulfonic acids and amines are regularly self-assembled by charge-assisted hydrogen bonding. Norimitsu Tohnai and co-workers demonstrate in their Research Article (e202202597) the advantages of diverse porous organic salts, such as all-organic, extremely facile preparation methods, diverse void structures and environments, and excellent CO2 adsorption properties.

An Eco-Friendly Tanning by Aromatic Sulphonic Acids for Enhancing Chrome Absorption and Reducing the Negative Impact on Environment

An Eco-Friendly Tanning by Aromatic Sulphonic Acids for Enhancing Chrome Absorption and Reducing the Negative Impact on Environment

Porous Organic Salts: Diversifying Void Structures and Environments.

Porous organic salts (POSs) are porous organic materials, in which various aromatic sulfonic acids and amines are regularly self-assembled by charge-assisted hydrogen bonding. POSs exhibit high solubility in highly polar solvents. Therefore, they are prepared via facile recrystallization and exhibit high recyclability. In this study, tetrahedral-structured tetrasulfonic acid and triphenylmethylamine (TPMA) were combined to construct POSs with rigid diamond networks called diamondoid porous organic salts (d-POSs). Furthermore, by introducing substituents (e.g., F, Cl, Br, or I) at the para-positions of benzene rings of TPMA, these substituents were exposed on the void surface of d-POSs, and their diamond networks were distorted. This induced the formation of a variety of void structures and environments in the d-POSs, which significantly affected their gas adsorption behavior. In particular, the d-POS from TPMA substituted by fluorine exhibited very high CO2 adsorption of 182 mL(STP) g-1 at 1 atm in all-organic porous materials.

Porous Organic Salts: Diversifying Void Structures and Environments

AbstractPorous organic salts (POSs) are porous organic materials, in which various aromatic sulfonic acids and amines are regularly self‐assembled by charge‐assisted hydrogen bonding. POSs exhibit high solubility in highly polar solvents. Therefore, they are prepared via facile recrystallization and exhibit high recyclability. In this study, tetrahedral‐structured tetrasulfonic acid and triphenylmethylamine (TPMA) were combined to construct POSs with rigid diamond networks called diamondoid porous organic salts (d‐POSs). Furthermore, by introducing substituents (e.g., F, Cl, Br, or I) at the para‐positions of benzene rings of TPMA, these substituents were exposed on the void surface of d‐POSs, and their diamond networks were distorted. This induced the formation of a variety of void structures and environments in the d‐POSs, which significantly affected their gas adsorption behavior. In particular, the d‐POS from TPMA substituted by fluorine exhibited very high CO2 adsorption of 182 mL(STP) g−1 at 1 atm in all‐organic porous materials.

High Proton Conductivity of 3D Graphene Oxide Intercalated with Aromatic Sulfonic Acids.

The development of efficient proton conductors that are capable of high power density, sufficient mechanical strength, and reduced gas permeability is challenging. Herein, we report the development of a series of aromatic sulfonic acid/graphene oxide hybrid membranes incorporating benzene sulfonic acid (BS), naphthalene sulfonic acid (NS), naphthalene disulfonic acid (DS) or pyrene sulfonic acid (PS) using a facile freeze dried method. For out-of-plane proton conductivity, the 3DGO-BS and 3DGO-NS yielded proton conductivities of 4.4×10-2 S cm-1 and 3.1×10-2 S cm-1 , respectively; this represents a two-times higher value than that which occurs for three dimensional graphene oxide (3DGO). Additionally, the respective prepared films as membranes in a proton exchange membrane fuel cell (PEMFC) show maximum power density of 98.76 mW cm-2 for 3DGO-NS while it is 92.75 mW cm-2 for 3DGO-BS which are close to double that obtained for 3DGO (50 mW cm-2 ).

New supramolecular hydrogen-bonded liquid crystals based on 4-alkylbenzenesulfonic acids and 4-pyridyl 4′-alkyloxybenzoates: Quantum chemical modeling and mesomorphic properties

• The new supramolecular liquid crystals with aromatic sulfonic acids were obtained. • Structural unit of systems under study is hydrogen-bonded complex. • Proton transfer occurs between sulfonic group and pyridyl fragment. • The results were confirmed by quantum chemistry, FTIR spectroscopy. • H-complexes formed by mesogen and nonmesogen have mesomorphic properties. The results of quantum-chemical modeling of the self-assembly process in the system based on 4-alkylbenzenesulfonic acids and 4-pyridyl 4′-alkyloxybenzoates are presented. It has been shown that the interaction of the pyridyl fragment of 4-pyridyl 4′-alkyloxybenzoat and the sulfonic group of 4-alkylbenzenesulfonic acid leads to the strongest H-complexes. The potential function of proton transfer from the sulfonic group to the pyridyl fragment was simulated both in the gas phase and in a solvent (ethanol). It was found that an H-complex with a hydrogen bond of the O∙∙∙H–N type is formed between the compounds under study. FTIR spectra of the 1(4-alkylbenzenesulfonic acid) : 1(4-pyridyl 4′-alkyloxybenzoate) systems confirm the results of quantum chemical calculations. The mesomorphic properties of the 1(4-methylbenzenesulfonic acid) : 1(4-pyridyl 4′-heptyloxybenzoate) supramolecular complex were studied using DSC and polarizing microscopy. It is shown that the H-complex formed by 4-methylbenzenesulfonic acid and 4-pyridyl 4′-heptyloxybenzoate has a smectic mesophase with expanded temperature range (59º) in comparison with the 4-pyridyl 4′-heptyloxybenzoate (28º).

Organo‐sulfonic acid catalyzed degradation kinetics and thermodynamic studies of nylon‐6 by hydrothermal method

AbstractNylon‐6 as an engineering polymer and its starting monomer are both costly. Chemical reutilization offers some economic and environmental benefits. Depolymerization of nylon‐6 was carried out by the conventional technique of hydrothermal method using various organo‐sulfonic acids such as Methane sulfonic acid (MSA), para‐toluene sulfonic acid (p‐TSA), benzene sulfonic acid (BSA), and tetra‐butyl ammonium bromide (TBAB) as a phase transfer catalyst. Various parameters such as temperature, time, normality of acids, and phase transfer catalyst concentration were varied to optimize its parameters, and characterization techniques such as amine value titrations and Fourier transform infrared spectroscopy were used for quantitative measurements. Solid‐state 13C NMR was done for structure confirmation. A chemical kinetics interpretation shows degradation mechanism follows first‐order kinetics under various catalysts. MSA has the highest reaction rate of 8.49 × 10−2 h−1 at 90°C; it decreases to 7.72 × 10−2 h−1 at 100°C. At the same time, aromatic Sulfonic acids such as p‐TSA and BSA have a higher reaction rate of 8.995 × 10−2 h−1 and 5.582 × 10−2 h−1, respectively. The activation energy was lowered as the acidity of organo‐sulfonic acids increased as benzene sulfonic acid has the lowest Ea. Followed by p‐TSA, and MSA has the highest Ea. Free energy shows a similar kind of value. A simple theoretical model was used to calculate the activation energy. Thermodynamic parameters such as heat of enthalpy and entropy of reaction were evaluated using the Eryig–Polanyi equation. The combined catalytic effect of organo‐sulfonic acids and phase‐transfer catalyst provides a better environment‐friendly method for depolymerizing nylon‐6.

Effect of Functional Groups on Chemical-Assisted MMP Reduction of a Methane-Oil System

Natural gas injection (i.e., recycling) is a commonly used for enhanced oil recovery method and is potentially cost-effective and efficient. However, natural gas injection, particularly methane, often has a high minimum miscibility pressure (MMP) which likely exceeds the fracture pressure of many otherwise viable reservoirs. Therefore, this work aims to investigate the potential of chemical-assisted MMP reduction of the methane-oil system to expand the application of miscible natural gas injection to more candidate reservoirs. In this context, we performed a study to test six potential surfactant-like chemicals with different polar headgroups (i.e., morpholine, aromatic sulfonic acid, aromatic carboxylic acid, and 2-oxypyrrolidine). The intent is to reduce the methane-oil interfacial tension using the vanishing interfacial tension method at a constant temperature of 373 K. First, at a concentration of 2 wt %, we tested the effect of the polar headgroups with the same hydrocarbon chain. Then, we investigated the effect of increasing the hydrocarbon chain length on the methane-oil miscibility. Our results show that chemical additives with the 2-oxopyrrolidine and aromatic sulfonic acid functional groups give higher MMP reductions (8.7–9.6%, respectively) compared with aromatic carboxylic acid and morpholine groups, which only give limited or no MMP reduction. Moreover, the results show that the reduction in first contact miscibility pressure is higher (12.8–19.1%) compared to MMP. Furthermore, increasing the hydrocarbon chain length (from 10 to 13) of the 2-oxopyrrolidine and aromatic sulfonic acid molecules seems to decrease the efficiency in reducing MMP. Our results screen the potential of a combinatorial chemistry approach (where two molecules with differing sizes and functional groups can be readily joined together to make a large library of compounds) that can be used to identify chemical additives for reducing MMP of methane-oil. This approach underscores the importance of optimizing the functional group and hydrocarbon chain length in potential chemicals for MMP reduction. The outlined research results likely expand the application of miscible natural gas injection to deep and/or high-temperature reservoirs, in addition to the environmental benefits of reducing gas flaring and greenhouse gas emissions through natural-gas recycling.

Mechanochemical sulfonation of aromatic compounds using NaHSO4·H2O/P2O5

A series of aromatic sulfonic acids is synthesized by subjecting arenes and NaHSO4·H2O to high-speed ball milling in the presence of P2O5. It is suggested the aromatic sulfonation occurs via in situ generated H2SO4 to give aromatic sulfonic acids. In some cases, formation of diaryl sulfones was observed.

Acid Hydrotropic Fractionation of Lignocelluloses for Sustainable Biorefinery: Advantages, Opportunities, and Research Needs.

This Minireview provides a comprehensive discussion on the potential of using acid hydrotropes for sustainably fractionating lignocelluloses for biorefinery applications. Acid hydrotropes are a class of acids that have hydrotrope properties toward lignin, which helps to solubilize lignin in aqueous systems. With the capability of cleaving ether and ester bonds and even lignin-carbohydrate complex (LCC) linkages, these acid hydrotropes can therefore isolate lignin embedded in the plant biomass cell wall and subsequently solubilize the isolated lignin in aqueous systems. Performances of two acid hydrotropes, that is, an aromatic sulfonic acid [p-toluenesulfonic acid (p-TsOH)] and a dicarboxylic acid [maleic acid (MA)], in terms of delignification and dissolution of hemicelluloses, and reducing lignin condensation, were evaluated and compared. The advantages of lignin esterification by MA for producing cellulosic sugars through enzymatic hydrolysis and lignin-containing cellulose nanofibrils (LCNFs) through mechanical fibrillation from the fractionated water insoluble solids (WIS), and for obtaining less condensed lignin with light color, were demonstrated. The excellent enzymatic digestibility of maleic acid hydrotropic fractionation WISs was also demonstrated by comparing with WISs from other fractionation processes. The recyclability and reusability of acid hydrotropes were also reviewed. Finally, perspectives on future research needs to address key technical issues for commercialization were also provided.

Sustainable design and novel synthesis of highly recyclable magnetic carbon containing aromatic sulfonic acid: Fe3O4@C/Ph—SO3H as green solid acid promoted regioselective synthesis of tetrazoloquinazolines

AbstractA green and stable magnetic Fe3O4 core encapsulated in porous carbon shell was prepared. Then, the surface of as‐synthesized Fe3O4@meso‐C immobilized with activated 4‐aminobenzenesulfonic acid to achieve Fe3O4@C/Ph—SO3H. Structural, physico‐chemical, and magnetic properties of synthesized Fe3O4@C/Ph—SO3H catalyst using various analyses such as FT‐IR spectroscopy, TGA, XRD, SEM, TEM. EDX, and VSM were investigated. Fe3O4@C/Ph—SO3H was used as a stable and recoverable acid catalyst for regioselective three‐component synthesis of tetrazoloquinazolines under mild conditions. This catalyst offers a green protocol of one pot due to having active SO3H groups, reacting in mild conditions with high yield and ability to recover and reuse without significant loss in activity.

Preparation of Functionalized Carbon-Coated Cobalt Nanoparticles with Sulfonated Arene Derivatives, a Study on Surface Functionalization and Stability.

The functionalization of magnetic nanoparticles has been an important field in the last decade due to the versatile applications in catalysis and biomedicine. Generally, a high degree of functionalities on the surface of the nanoparticles is desired. In this study, covalent functionalization of various aromatic sulfonic acids on carbon-coated cobalt nanoparticles are investigated on surface functionalization yield and stability. The nanoparticles are prepared via covalent linkage of an in situ generated diazonium on the graphene-like surface. Adsorption and wash experiments were performed to confirm a covalent bonding of the naphthalene derivatives on the nanoparticle surface. With an increased number of sulfonic acid groups on the aromatic compound a significantly lower loading is observed on the corresponding functionalized nanoparticles. This can be counteracted by a change of nitrite species. With this method, nanoparticles with a high number of sulfonic acid groups can be produced.

ИОНООБМЕННЫЕ МАТЕРИАЛЫ НА ОСНОВЕ ПРОМЫШЛЕННОГО ПОЛИВИНИЛХЛОРИДА

The possibility of modifying polyvinyl chloride with aromatic sulfonic acids in order
 to obtain proton-conducting membranes for fuel cells was discussed.